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Gas‐phase ion‐molecule reaction of alpha‐phenylvinyl cation towards substituted benzenes in the environment of an ITMS
Author(s) -
Begala Michela,
Tocco Graziella
Publication year - 2011
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.1997
Subject(s) - chemistry , substituent , heteroatom , electron ionization , molecule , ion , dissociation (chemistry) , mass spectrometry , selectivity , alkylation , medicinal chemistry , ionization , chemical ionization , polyatomic ion , organic chemistry , ring (chemistry) , catalysis , chromatography
Ion‐molecule reactions between the α‐phenylvinyl cation (α‐PVC) and mono‐substituted benzenes have been investigated using a quadrople ion‐trap mass spectrometer. The α‐PVC, generated by chemical ionization from phenylacetilene, was found to react selectively with mono‐substituted benzenes bearing electron withdrawing groups to give the product ions [M + 103] + and the trans ‐vinylating product ions [M + 25] + . To characterize the reaction products, a combination of collision‐induced dissociation, isotope‐labeling experiments and model compounds were used. The results indicate, in addition to direct heteroatom alkylation, high extent of ortho attack. We attributed the positional selectivity of the α‐PVC to the nature of the substituent on the neutral molecule. In particular, hydroxy and amino groups promoted the alkenylation at ortho position. Copyright © 2011 John Wiley & Sons, Ltd.